Chapter 9

1. Determine the DG' of the reaction:

malate + NAD+

oxaloacetate + NADH + H+

The two half reactions from the half reaction table are:

(1)

oxaloacetate + 2 H+ + 2 e

(2)

NAD+ + 2H+ + 2 e

malate

E' = 0.175 V

NADH + H+

E' = 0.320 V

First, we need to find the DE' of the reaction:

The overall reaction consists of half reaction (2) added to the reverse of half reaction (1):

malate + NAD+ + 2H+ + 2e

oxaloacetate + NADH + H+ + 2H+ + 2e

Looking at the overall reaction, we can see that half reaction (2) functions as the
reduction reaction (NAD+gains electrons), and half reaction (1) functions as the oxidation
reaction (malate loses electrons). TheDE' for the reaction is therefore

DE' = (E' from reduction

DE'
=
(0.320
DE' = 0.145 V

reaction)
V)

(E'

from
(

oxidation reaction)
0.175
V)

Then, use the formula to calculate DG' :

DG'
DG'
=
DG'
DG' = 28 kJ

=
mol)(96,500

(2
=

nF(DE')
J/V/mol)(0.145
V)
27,985
J

2. Balance the two half reactions for the reaction in an acid solution:

H2O2 + I- =

I2 + H2O

I- is
oxidized
(oxidation
state
increases
from
O (oxygen) is reduced (oxidation state decreases from -1 to -2).

-1

to

0).

The two half-reactions with balanced number of key atoms are:

2
I=
I2;
H2O2 = 2 H2O <--- (reduction of oxygen)

<---

(oxidation)

Add electrons to compensate for the changes of oxidation state

2
I=
H2O2 + 2 e = 2 H2O (reduction)

I2 +

e- (oxidation)

Obviously, H+ should be added to the reduction half-reaction, and the balanced

equations are:
2 I- = I2; <--- (oxidation)
3. Balance two half reactions for the reaction in a basic solution:
ClO2 + OH- = ClO2- + ClO3In this reaction, Cl from ClO2 is both oxidized and reduced.
The two half-reactions are:
ClO2 = ClO2-;
ClO2 = ClO3-; (oxidation)
Add electrons to compensate for the oxidation changes:

(reduction)

ClO2 +
e- = ClO2-;
(reduced,
ClO2 = ClO3 + e ; (oxidized, 4 -> 5)

->

for

Cl)

Add H+, OH-, or H2O to balance both equations results in

ClO2 +
ClO2 + 2 OH- = ClO3- + e- + H2O

e- = ClO2-

Now add the two half reactions together to give the overall reaction:
2 ClO2 + 2 OH- = ClO2- + ClO3- + H2O
4. Calculate the cell potential in the following redox reaction under standard conditions:
Fe3+(aq)+V2+(aq)Fe2+(aq)+V3+(aq)
SOLUTION
Consult the table of standard reduction potentials (Table P1) for each half reaction:
Fe3+(aq)+eFe2+(aq)with Eo=0.771V
V2+(aq)V3+(aq)+ewith Eo=0.255V
The cell potential is
Eocell=EocathodeEoanode=0.771V(0.255V)=1.026V
5. balanced reaction in basic solution
10I- (aq) + 2MnO4- (aq) + 16H+ (aq) + 16OH- (aq) 5I2 (s) + 2Mn2+ (aq) + 8H2O (l)
+ 16OH- (aq)
10I- (aq) + 2MnO4- (aq) + 16H2O (l) 5I2 (s) + 2Mn2+ (aq) + 8H2O (l) + 16OH- (aq)
Eight water molecules can be canceled, leaving eight on the reactant side:
10I- (aq) + 2MnO4- (aq) + 8H2O (l) 5I2 (s) + 2Mn2+ (aq) + 16OH- (aq)
This is the balanced reaction in basic solution.

Electro chemical cell potential

Example: Find the standard cell potential for an electrochemical cell with the
following cell reaction.
Zn(s) + Cu2+(aq)

Zn2+(aq) + Cu(s)

Write the half-reactions for each process.

Zn(s)

Zn2+(aq) + 2 e-

Cu2+(aq) + 2 e-

Cu(s)

Look up the standard potentials for the redcution half-reaction.

Eoreduction of Cu2+ = + 0.339 V
Look up the standard reduction potential for the reverse of the oxidation
reaction and change the sign.
Eoreduction of Zn2+ = - 0.762 V
Eooxidation of Zn = - ( - 0.762 V) = + 0.762 V
Add the cell potentials together to get the overall standard cell potential.
Zn2+(aq) + 2 e-

oxidation:

Zn(s)

reduction:

Cu2+(aq) + 2 e-

overall:

Zn(s) + Cu2+(aq)
Cu(s)

Cu(s)
Zn2+(aq) +

Eoox. = - Eored. = - (- 0.762 V) = +

0.762 V
Eored. = + 0.339 V
Eocell = + 1.101 V

Calculations in electrochemical and Electrolytic cells

Electrochemical Calculations
1) Calculations of equilibrium constants from tables of reduction potentials.
What is the K for ceric oxidation of ferrous iron?
The full reaction,

is comprised of the two half reactions

The E are found from the table of reduction potentials in the back of the book. Notice
that when the reaction is reversed, as for Fe2+ oxidation, the sign of E is changed. The
sum of the two half reactions yields the total reaction and the reaction potential is the sum
of the two half reaction potentials
E = 1.63 V - 0.77 V = +0.86 V
Using the formulas,
DGo= -nFE
DG = -(1)(96,500 Coul/mole)(0.86 V)
DG = -83 kJ/mole
DG = -RT ln K
-83 kJ/mole = -(8.314 J/mole K)(298 K) ln K
K = 3.5 1014

Electrochemical Calculations
Calculations of electrode potentials for electrodes using insoluble salts.
Q: What is the electrode potential for the electrode Ag/AgI(s)/I- (0.01 M) ?
A: The overall reaction for this electrode is

This reaction cannot be found in most tables of reduction potentials. But the reaction is
comprised of two components,

We can find the E for the solubility product equilibrium from DG =kTlnKsp and
DG =-nFE

0.059log is valid at room temperature. In this case

E = .059 log Ksp = .059 log 10-16 = (.059)(-16) = -0.9 V
The electrode potential is E =E red+E Ksp = 0.8V-0.9V = -0.1V
Now we use the Nernst Equation to find the electrode potential

E = E - .059 log [I-]

E = -0.1V - .059 log 10-2
E = -0.1V - .059(-2) .02 V

Electrochemical Calculations
Typical Examples
2) Another way to look at the electrode potential for Ag/AgI(s)/I-(0.01 M)
The overall reaction for this electrode is

The reaction is comprised of two components,

Note the change of sign on the E because it is an oxidation. We can initially ignore the
fact that the electrode contains AgI and find E for the silver ion reduction.

The electrode potential is based on the concentration of Ag+ in solution. Since

and

In this case
In either calculation, the important point to recognize is that the electrode contains an
insoluble salt.

Calculating the Cell Potential:

The net reaction of a voltaic cell constructed from a standard zinc electrode and a standard
copper electrode is obtained by adding the two half-reactions together:
Zn2+(aq) + 2e

oxidation

Zn(s)

reduction

2 [ 1 e + Ag+(aq)

E = 0.763 V

Ag (s) ]

E = 0.337 V
sum

Zn(s) + 2 Ag+(aq)

net

2 Ag(s) + Zn2+(aq)

E = 1.100 V

Calculate Eocell for the following redox reaction under standard conditions:
2Al(s) + 3Sn2+(aq) 2Al3+(aq) +3Sn(s)
Oxidation:{Al(s) Al3+(aq) +3e-} x 2
Reduction:{Sn2+(aq) +2e- Sn(s)} x 3
Net:2Al(s) + 3Sn2+(aq) 2Al3+(aq) + 3Sn(s)

-Eo = +1.676V
Eo = -0.137V
Eocell = -0.137V - (-1.676V)

Eocell= +1.539 V.
Balance the following reaction in an acidic aqueous solution:
MnO-4 +H2C2O4Mn2++CO2

Reduction half-reaction:
2(5e + 8H+ + MnO4 Mn2+ + 4H2O)

Oxidation half-reaction:
5(H2C2O4 CO2+2H++2e)
10e+16H++2MnO41 +5H2C2O4 2Mn2+ +8H2O +10CO2+10H++10e
Answer:

Questions

6H+ + 2MnO4- + 5H2C2O4 2Mn2+ + 8H2O +10CO2

1. Determine the new cell potential resulting from the changed conditions.
o Calculate the value for the reaction quotient, Q. (Note: We calculate Q
using molar concentrations for solutions and pressures for gases. Water
and bromine are both liquids, therefore they are not included in the
calculation of Q.)

o Calculate the number of moles of electrons transferred in the balanced

equation, n.
n = 4 moles of electrons
o Substitute values into the Nernst equation and solve for the non-standard
cell potential, Ecell.
Ecell
=
+
Ecell = 0.063 V

0.152

(0.0257/4)

ln(1.02

10 6)

2. Calculate the solubility product of AgI at 25.0 C, given the following data:
Reduction half-reaction
AgI(s) + e ---> Ag(s) + I
I2(s) + 2e ---> 2I
Ag+ + e ---> Ag(s)

E (V)
-0.15
-0.54
0.80

Solution:
)The chemical equation for AgI dissolving is:
AgI(s) Ag+(aq) + I(aq)
and the Ksp expression is:

The equations to use are:

Ksp = [Ag+] [I]

E (V)
-0.15
-0.80

AgI(s) + e ---> Ag(s) + I

Ag(s) ---> Ag+ + e
Yielding E = -0.95 V
Use the Nernst Equation:
Ecell = E - (0.0591 / n) log K
0 = -0.95 - (0.0591 / 1) log K
0.95 / -0.0591 = log K
log K = -16.07
K = 8.51 x 1017

3. Using the following reduction potentials, calculate the solubility product for
AgCN at 298 K:
Ag+ + e ---> Ag
AgCN + e ---> Ag + CN

E = 0.80 V
E = -0.01 V

Solution:
Reverse first half-reaction:
Ag ---> Ag+ + e
AgCN + e --> Ag + CN

E = -0.80 V
E = -0.01 V

Add:
AgCN ---> Ag+ + CN

E = -0.81 V

Use -RT ln K = -nFE

(8.314) (298) ln K = (1) (96485) (-0.81)
ln K = -31.544
Ksp = 2.0 x 10-14

A zinc electrode is submerged in an acidic 0.80 M Zn2+ solution which is connected by a

salt bridge to a 1.30 M Ag+ solution containing a silver electrode.
E0red: Zn2+aq + 2e- Zns = -0.76 V

E0red: Ag+aq + e- Ags = +0.80 V

Ecell = E0cell - (0.0591 V/n)log Q
Q = [Zn2+]/[Ag+]2
4.

The reaction proceeds spontaneously so E 0 is positive. The only way for that to
occur is if Zn is oxidized (+0.76 V) and silver is reduced (+0.80 V). Once you
realize that, you can write the balanced chemical equation for the cell reaction and
can calculate E0:
Zns Zn2+aq + 2e- and E0ox = +0.76 V

2Ag+aq + 2e- 2Ags and E0red = +0.80 V

which are added together to yield:
Zns + 2Ag+aq Zn2+a + 2Ags with E0 = 1.56 V
Now, applying the Nernst equation:
Q = (0.80)/(1.30)2
Q = (0.80)/(1.69)
Q = 0.47
E = 1.56 V - (0.0591 / 2)log(0.47)
E = 1.57 V

5. Calculate the change in Gibbs free energy of an electrochemical cell where the
following redox reaction is taking place:

Pb2++NiNi2++Pb

Eo=0.12 V

To solve, we need to use the equation:

Go=nFEo
The number of moles of electrons transferred is 2, while the cell potential is equal to 0.12
V. One volt is 1JouleCoulomb.

Go=2 moles e96485Coulombsmole0.12JoulesCoulomb

Go=23,156 J =2.3 kJ